Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
  • C07D235/08—Radicals containing only hydrogen and carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
  • C07D235/10—Radicals substituted by halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D235/26—Oxygen atoms

Definitions

• the present invention relates to the use of benzimidazole derivatives as performance promoters for animals, new benzimidazole derivatives and intermediates and processes for their preparation.
• Some of the compounds of the formula I are known.
• the known compounds have a bronchodilatory effect. They also lower intraocular pressure.
• Compounds of the formula I can be used as performance promoters in animals and particularly to promote growth in animals.
• the compounds of the formula I can also be present in the form of their racemates and as mixtures of the mutually diastereomeric or enantiomeric forms.
• Physiologically acceptable salts of the compounds of the formula I can be formed with the following acids: Hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, bromic acid, hydroiodic acid, nitric acid, acetic acid, oxalic acid, malonic acid, succinic acid, ascorbic acid, Malic acid, tartaric acid, maleic acid, fumaric acid, methanesulfonic acid, benzoic acid, substituted benzoic acids, formic acid, toluenesulfonic acid, benzenesulfonic acid, phthalic acid, naphthalenesulfonic acid, nicotinic acid, palmitic acid, embonic acid.
• R1 represents H, OH
• R2 represents H, halogen, CN, haloalkyl
• R3 stands for H
• R4 is H, C1 ⁇ 4 alkyl
• R5 represents C1 ⁇ 4 alkyl
• R6 for C1 ⁇ 4-alkyl, optionally substituted by halogen, OH, C1 ⁇ 4-alkoxy, C1 ⁇ 4-haloalkoxy, phenyl, which is optionally substituted by C1 ⁇ 4-alkyl, COR7, -O-C1 ⁇ 3-alkylene-COR7 , C1 ⁇ 3-alkylene-R8, O-C1 ⁇ 3-alkylene-R8 is substituted
• R7 represents OH, C1 ⁇ 4 alkoxy, amino, methylamino, dimethylamino
• R8 represents OH, C1 ⁇ 4 alkoxy, amino, methylamino, dimethylamino.
• R1 represents hydrogen or OH
• R2 represents hydrogen, chlorine, bromine, trifluoromethyl
• R3 represents hydrogen
• R4 represents hydrogen or methyl
• R5 represents methyl
• R6 represents methyl, which is optionally substituted by OH or phenyl, which in turn is optionally substituted by methyl, ethyl, methoxyethyl, hydroxyethyl, methoxyethyloxy, hydroxyethyloxy.
• the new compounds of the formula I can be prepared by the processes given under 3 a - d.
• process 3a) If 4-chlorobenzimidazoyl-6-bromomethyl ketone is used in process 3a) as compound of formula II and tert-butylamine as amine of formula III, process 3a) can be represented by the following scheme:
• the compounds of formula II are partly new. Their manufacture is described below.
• the substituents R 1 and R 2 preferably have the preferred meanings given above.
• the following compounds of the formula II may be mentioned in particular: Benzimidazoyl-5-bromomethyl ketone Benzimidazoyl-5-chloromethyl ketone 4-bromobenzimidazoyl-6-bromomethyl ketone 4-bromobenzimidazoyl-6-chloromethyl ketone
• the amines of the formula III are known (cf., for example, EP-OS 23,385).
• the substituents R4 to R6 preferably have the preferred meanings mentioned above for the compounds of the formula I.
• the following amines of the formula III may be mentioned: Isopropylamine Isobutylamine sec. butylamine tert.
• Butylamine 2-amino-2-methyl-propanol-1 3- (4-carbomethoxyphenyl) -2-propylamine, 3- (4-methoxycarbonylmethoxyphenyl) -2-propylamine, 3- (4-carboxyphenyl) -2-propylamine, 3- (4-carboxymethoxyphenyl) -2-propylamine, 3- (4-hydroxymethylphenyl) -2-propylamine, 3- (4-dimethylaminomethylphenyl) 2-propylamine, 3- (4- (2-Hydroxyethyl) phenyl) -2-propylamine.
• reducing agents may be mentioned as reducing agents for carrying out process 3a): H2 / catalyst, the following may be mentioned as catalysts: PtO2, Pd activated carbon; complex metal hydrides such as LiAlH4, NaBH4, NaBH3CN.
• NaBH4 and NaBH3CN Process 3a is carried out by combining the compounds II and III in a diluent in an approximately equimolar ratio and then reducing them.
• the reduction is preferably carried out at temperatures from -20 ° C. to + 100 ° C.
• inert organic solvents are used as diluents. These include in particular aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene; chlorinated hydrocarbons such as methylene chloride, ethylene chloride, chloroform; Ethers such as diethyl ether and glycol dimethyl ether; Nitriles such as acetonitrile, propionitrile and Benzonitrile; Alcohols such as methanol, ethanol, n- and i-propanol.
• aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene
• chlorinated hydrocarbons such as methylene chloride, ethylene chloride, chloroform
• Ethers such as diethyl ether and glycol dimethyl
• Alcohols are preferred, and the reduction can be carried out immediately without isolating the intermediates.
• method 3b uses 1- (5-benzimidazoyl) -1-hydroxy-2-chloroethane as the compound of formula IV and 3- (4-carbomethoxyphenyl) -2-propylamine as the amine of formula III, method 3b can be used ) by the following scheme:
• ⁇ -haloethyl compounds of the formula IV are new. Their manufacture is described below.
• the substituents R 1 to R 3 preferably have the preferred meanings given for the compounds of the formula I.
• the following compounds of the formula IV may be mentioned individually: 1- (5-benzimidazoyl) -2-chloroethanol 1- (5-benzimidazoyl) -2-bromoethanol 1- (4-bromo-6-benzimidazoyl) -2-chloroethanol 1- (4-bromo-6-benzimidazoyl) -2-bromoethanol 1- (4-chloro-6-benzimidazoyl) -2-bromoethanol
• Process 3b) is carried out by reacting the ⁇ -haloethyl compound of the formula IV with excess amine of the formula III, if appropriate in the presence of a diluent.
• the reaction is carried out at temperatures from +20 to + 150 ° C.
• inert organic solvents are used as diluents. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, furthermore nitriles such as acetonitrile and benzonitrile, furthermore amides such as dimethylformamide, furthermore alcohols such as methanol , Ethanol, n- and 1-propanol.
• halogenated hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, furthermore nitrile
• Alcohols are preferably used.
• process 3c 1- (5-benzimidazoyl) -2-aminoethanol is used as the compound of the formula V and as the compound of formula VI 4- (dimethylaminomethyl) phenylacetone, process 3c) can be represented by the following reaction scheme:
• Process 3c) is carried out by initially introducing approximately equimolar amounts of the compounds of the formulas V and VI into a diluent and reducing the mixture.
• the reaction is carried out at temperatures from 0 ° C to 150 ° C.
• inert organic solvents are used as diluents. These include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, ethylene chloride, chloroform, chlorobenzene, furthermore ethers such as diethyl ether, tetrahydrofuran, dioxane, furthermore nitriles such as acetonitrile, benzonitrile, amides such as dimethylformamide, alcohols such as Methanol, ethanol.
• aliphatic and aromatic optionally halogenated hydrocarbons
• halogenated hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, ethylene chloride, chloroform, chlorobenzene, furthermore ethers such as diethyl ether, te
• H2 / catalyst for example PtO2 may be mentioned; complex metal hydrides such as B. LiAlH4, NaBH4, NaBH3CN.
• process 3d) uses 5-benzimidazoylglyoxal as the compound of the formula VII and 3- (4-methoxyphenyl) -2-propylamine as the amine of the formula III, process 3d) can be represented by the following reaction scheme:
• Process 3d) is carried out by adding about the equivalent amount of the amine of the formula III to the compound of the formula VII in a diluent and then reducing it.
• the reaction is carried out at temperatures from 0 ° C to 100 ° C.
• inert organic solvents are used as diluents. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, also esters, such as methyl acetate and ethyl ester, and also nitriles, such as.
• aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum
• B acetonitrile and propionitrile, benzonitrile, glutaronitrile, and also amides, such as. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and tetramethylene sulfone and hexamethylphosphoric triamide, alcohols such as methanol, ethanol, n- and i-propanol.
• PtO2 and Pd carbon may be mentioned as catalysts; also complex metal hydrides such as LiAlH4 and NaBH4.
• the new compounds of the formula II can be prepared by the processes given under 5.
• Process 5a) is carried out by adding the equivalent amount of halogen, possibly dissolved in a diluent, to compound VIII in a diluent.
• the reaction is carried out at + 20 ° C to + 150 ° C, preferably at the boiling point of the diluent used.
• diluents aliphatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, alcohols such as methanol, ethanol, esters such as ethyl acetate and mixtures of these diluents.
• Process 5b) is carried out by refluxing equivalent amounts of the compound of the formula VIII and the compound CuHal2 in the diluent for 1 to 24 h, preferably 6 to 12 h.
• the new compounds of the formula VIII can be prepared by the process indicated under 7.
• the radical R2 preferably has the meaning hydrogen, C1 ⁇ 4-alkyl in particular methyl, chlorine, bromine.
• the following compounds of the formula IX may be mentioned individually: 3-bromo-4,5-diaminoacetophenone 3-chloro-4,5-diaminoacetophenone
• the process is carried out by reacting a compound of the formula IX with formic acid in the presence of an inorganic acid.
• the inorganic acids include hydrohalic acids such as hydrochloric acid, sulfuric acid, phosphoric acid.
• the reaction is carried out at temperatures from + 20 ° C to + 120 ° C.
• the new compounds of the formula IV can be prepared by the process specified under 9.
• H2 / catalyst may be mentioned as a catalyst: PtO2, Pd / coal; complex metal hydrides, e.g. LiAlH4, NaBH4, NaBH3CN. NaBH4 and NaBH3CN are preferably used.
• the process is carried out by reacting the compound II with the reducing agent in a diluent.
• the reaction is carried out at temperatures from -20 ° C to + 100 ° C.
• inert organic solvents are used as diluents. These include, in particular, optionally halogenated aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, chlorobenzene; Ethers such as diethyl ether, tetrahydrofuran; Nitriles such as acetonitrile, benzonitrile, alcohols such as methanol, ethanol, n- and i-propanol. Alcohols are preferably used.
• optionally halogenated aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, chlorobenzene
• Ethers such as diethyl ether, tetrahydrofuran
• Nitriles such as acetonitrile,
• the new compounds of the formula VII can be prepared by the processes specified under 13.
• the compounds mentioned above are preferably used as halogenomethyl ketones of the formula II.
• Process 13a) is carried out by oxidizing the compounds of the formula II, if appropriate in the presence of a diluent.
• the reaction is carried out at temperatures from + 20 ° C to + 100 ° C.
• Dimethyl sulfoxide is preferably used as the oxidizing agent (N. Kornblum et. Al., JACS 79 , 6562 (1957)).
• inert organic solvents can be used. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, chlorobenzene; Ethers such as diethyl ether, tetrahydrofuran; Nitriles such as acetonitrile, benzonitrile. It is preferred to work in dimethyl sulfoxide without another solvent.
• the process is carried out by oxidizing the compound of the formula VIII with selenium dioxide in the presence of a diluent (cf. Org. React. 5 (1949), 331).
• the active ingredients are suitable as a means of promoting performance in breeding and farm animals. They serve to promote and accelerate growth, milk and wool production, as well as to improve feed utilization, meat quality and to shift the meat-fat ratio in favor of meat.
• the livestock and breeding animals include mammals such as B. cattle, horses, sheep, pigs, goats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer, fur animals such. B. mink, chinchilla, raccoon, birds such. B. chickens, geese, turkeys, ducks, fresh and saltwater fish such. B. trout, carp, eels.
• the active ingredients are used regardless of the sex of the animals during all growth and performance phases of the animals.
• the active ingredients are preferably used during the intensive growth and performance phase.
• the intensive growth and performance phase lasts from one month to 10 years, depending on the animal species.
• the active ingredients prove to be particularly valuable in the rearing and keeping of young and fattening animals.
• the active ingredients are used directly or in the form of enteral or animal-friendly preparations parenteral.
• the enteral application of the active ingredients happens, for. B. orally in the form of powders, tablets, capsules, pastes, drinkers, granules, boluses, orally administrable solutions, emulsions or suspensions and the feed or drinking water.
• the parenteral application happens for. B. in the form of injection (intramuscular, subcutaneous, intravenous or through implants).
• compositions for administration via feed or drinking water are particularly emphasized.
• the active ingredients can be added to the feed directly or in the form of premixes or feed concentrates.
• the feed includes single feed of vegetable origin such as hay, beets, cereals and grain by-products, molasses, silage, single feed of animal origin such as meat, fats, milk products, bone meal, fish products, the single feed such as vitamins, proteins, sugar, starch, flours, amino acids e.g. B. DL-methionine, salts such as lime and common salt.
• the feed also includes supplementary, finished and compound feed. These contain feed materials in a composition that ensures a balanced diet in terms of energy and protein supply as well as the supply of vitamins, mineral salts and trace elements.
• Premixes and feed concentrates are mixtures of the active ingredient with carriers and, if necessary, other ones Auxiliary materials.
• the carrier substances include all feed materials or mixtures thereof.
• the active ingredients can be present in the preparations alone or in mixtures with other performance-enhancing active ingredients, mineral feed, trace element compounds, vitamins, nitrogen-containing non-protein compounds, dyes, antioxidants, flavorings, emulsifiers, flow aids, preservatives and pressing aids.
• performance-enhancing active ingredients are e.g. B. antibiotics such as tylosin and virginamycin.
• Mineral feeds are e.g. B. dicalcium phosphate, magnesium oxide, sodium chloride.
• Trace element compounds are e.g. B. iron fumarate, sodium iodide, cobalt chloride, copper sulfate, zinc oxide, selenium compounds.
• Vitamins are e.g. B. Vitamin A, Vitamin D3, Vitamin E.
• Nitrogen-containing non-protein compounds are e.g. B. biuret, urea.
• Dyes are e.g. B. carotenoids such as canthaxidine, zeaxanthin, capsanthin or dyes that are approved for coloring food.
• Antioxidants are e.g. B. ethoxyquin, butylhydroxy-toluene, ascorbic acid.
• Flavorings are e.g. B. Vanillin.
• Emulsifiers are e.g. B. Lactic acid esters, lecithin.
• Industrial additives are e.g. As sodium stearate, calcium stearate, silicas, bentonites, lignin sulfonates.
• Preservatives are e.g. B. propionic acid, calcium propionate, sorbic acid, ascorbic acid. Pressing aids are e.g. B. lignin sulfonates, cellulose ethers.
• the concentration of the active ingredients in the feed is normally about 0.001-500 ppm, preferably 0.1-50 ppm.
• the concentration of the active ingredients in the premixes or feed concentrates is approximately 0.5 to 50 percent by weight, preferably 1 to 20 percent by weight.
• the amount of active ingredients that are administered to the animals to achieve the desired effect can be varied widely because of the favorable properties of the active ingredients. It is preferably about 0.001 to 50 mg / kg, in particular 0.01 to 5 mg / kg of body weight per day.
• the appropriate amount of the active ingredient and the appropriate duration of administration depend in particular on the type, age, gender, state of health and the type of keeping and feeding the animals and are easy to determine by any person skilled in the art.
• the active substances are administered to the animals according to the usual methods.
• the method of administration depends in particular on the type, behavior and state of health of the animals.
• the active substances can be administered once.
• the active ingredients can also during the whole or during part of the growth and performance phase be administered temporarily or continuously. With continuous administration, the application can take place once or several times a day at regular or irregular intervals.
• Example of the composition of a chick rearing feed containing the active ingredient according to the invention 200 g wheat, 340 g corn, 361 g soybean meal, 60 g beef tallow, 15 g dicalcium phosphate, 10 g calcium carbonate, 4 g iodized table salt, 7.5 g vitamin-mineral mixture of the composition given below and 2.5 g active ingredient premix the below After careful mixing, the stated composition gives 1 kg of feed.
• vitamin-mineral mixture contains: 600 I.U. Vitamin A, 100 IU Vitamin D3, 10 mg vitamin E, 1 mg vitamin K3, 3 mg riboflavin, 2 mg pyridoxine, 20 mcg vitamin B12, 5 mg calcium pantothenate, 30 mg nicotinic acid, 200 mg choline chloride, 200 mg MnSO4 x H2O, 140 mg ZnSO4 x 7 H2O , 100 mg FeSO4 x 7 H2O and 20 mg CuSO4 x 5 H2O in cereal flour as a carrier.
• 1 kg of active ingredient premix contains 100 g of active ingredient, 900 g of wheat flour.
• Example of the composition of a pig rearing feed containing the active ingredient according to the invention 630 g of feed grain meal (composed of 200 g corn, 150 g barley, 150 g oat and 130 g wheat meal), 80 g fish meal, 60 g soybean meal, 60 g tapioca flour, 38 g brewer's yeast, 50 g vitamin-mineral mixture (composition as for chick feed) 30 g linseed cake flour, 30 g corn gluten feed, 10 g soybean oil, 10 g sugar cane molasses and 2 g After thorough mixing, the active ingredient premix gives 1 kg of feed. 1 kg of active ingredient premix contains 200 g of active ingredient, 20 g of vegetable oil, 780 g of calcium carbonate powder.
• Example of the composition of a feed for cattle containing the active ingredient according to the invention 69.95% feed grain meal, 10% ground corn on the cob, 8% soybean flour, 5% lucerne flour, 5% molasses, 0.6% urea, 0.5% calcium phosphate, 0.5% calcium carbonate, 0.3% table salt, 0.15 % Vitamin-mineral mixture and 0.2% active ingredient premix of the composition given for pig rearing feed.
• the vitamin-mineral mixture contains 70,000 iE vitamin A, 70,000 vitamin D3, 100 mg vitamin E, 50 mg MnSO4 x H2O, 30 mg ZnSO4 x 7H2O in cereal flour as a carrier per kg.
• the premix of active ingredients is added to the vitamin-mineral mixture in the required amount and then carefully mixed with the other ingredients.
• mice Female laboratory rats weighing 90-110 g of the type SPF Wistar (breed Hagemann) are fed ad lib with standard rat food, which is mixed with the desired amount of active ingredient. Each test batch is carried out with feed from the same batch, so that differences in the composition of the feed cannot impair the comparability of the results.
• the rats receive water from lib.
• rats form a test group and are fed with feed mixed with the desired amount of active ingredient.
• a control group receives feed without active ingredient.
• the test groups are put together in such a way that the average body weight and the scatter in the body weights of the rats are the same in each test group, so that the test groups can be compared with one another.
• the animals are adapted to the new husbandry conditions for 2 days before the start of the experiment, during which time feed is given without the addition of active ingredients.
• the animals are then fed food containing the active ingredient for 13 days.
• the relative weight gain in relation to the untreated control is determined.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fodder In General (AREA)

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• 1988
  • 1988-01-05 DE DE3800096A patent/DE3800096A1/de not_active Withdrawn
  • 1988-12-22 NZ NZ227460A patent/NZ227460A/en unknown
  • 1988-12-23 AU AU27528/88A patent/AU2752888A/en not_active Abandoned
  • 1988-12-27 JP JP63328077A patent/JPH02138264A/ja active Pending
  • 1988-12-30 EP EP88121880A patent/EP0325802A1/fr not_active Withdrawn
  • 1988-12-30 IL IL88847A patent/IL88847A0/xx unknown
  • 1988-12-30 US US07/292,581 patent/US4960783A/en not_active Expired - Fee Related
• 1989
  • 1989-01-04 PL PL1989277049A patent/PL154143B1/pl unknown
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  • 1989-01-05 KR KR1019890000023A patent/KR890011858A/ko not_active Application Discontinuation
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